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WO1997013809A1 - Composition thermodurcissable, procede de revetement de finition et articles comportant ce revetement - Google Patents

Composition thermodurcissable, procede de revetement de finition et articles comportant ce revetement Download PDF

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Publication number
WO1997013809A1
WO1997013809A1 PCT/JP1996/002971 JP9602971W WO9713809A1 WO 1997013809 A1 WO1997013809 A1 WO 1997013809A1 JP 9602971 W JP9602971 W JP 9602971W WO 9713809 A1 WO9713809 A1 WO 9713809A1
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WO
WIPO (PCT)
Prior art keywords
group
component
compound
acid
oxide sol
Prior art date
Application number
PCT/JP1996/002971
Other languages
English (en)
Japanese (ja)
Inventor
Toshio Yamamoto
Masahiro Sano
Hiroki Mizutani
Keiji Komoto
Masahiro Ishidoya
Original Assignee
Nof Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nof Corporation filed Critical Nof Corporation
Priority to EP96933638A priority Critical patent/EP0805186B1/fr
Priority to KR1019970702389A priority patent/KR100237105B1/ko
Priority to DE69621423T priority patent/DE69621423T2/de
Priority to US08/849,545 priority patent/US6103387A/en
Priority to CA002207790A priority patent/CA2207790C/fr
Priority to JP51013697A priority patent/JP3931348B2/ja
Publication of WO1997013809A1 publication Critical patent/WO1997013809A1/fr
Priority to KR1019997004669A priority patent/KR100237104B1/ko

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31533—Of polythioether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31794—Of cross-linked polyester

Definitions

  • the present invention relates to a thermosetting dangling composition, a coating finishing method, and a coated article. More specifically, the present invention provides a cured product containing a ceramic component and having excellent stain resistance, stain removal properties, weather (light) resistance, chemical resistance, moisture resistance and appearance, and environmental protection. The present invention relates to a thermosetting composition, a paint finishing method, and a painted article having high safety and high safety.
  • thermosetting composition comprising a combination with a compound having an isocyanate group, a blocked isocyanate group, a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group or a ketal group. Things are known.
  • a composition comprising a combination of a carboxyl group and an epoxy group is disclosed in Japanese Patent Laid-Open Publication No. 51-144429, European Patent Publication No. 29,595, US Pat. Patents 4,371,667, 4,650,718, 4.681,811, 4,703,101, and 4,764,430 .
  • compositions comprising a combination of a carboxyl group and an oxazoline group are described in U.S. Pat. No. 3,505,297, JP-A-60-88038 and JP-A-2-1-15238 of Japanese Patent Publications. It has been published.
  • thermosetting compositions are widely used in the fields of paints, inks, adhesives, and plastic moldings, for example, because of the excellent chemical performance, physical performance, and weather resistance of the resulting cured products. It's being used.
  • carboxyl group and the reactive functional group have high reactivity, a composition in which a carboxyl group-containing compound and a compound containing the reactive functional group coexist may cause gelation during storage. This causes problems such as shortened pot life.
  • the carboxyl group-containing compound used in the conventional thermosetting composition has low solubility in general-purpose organic solvents due to strong hydrogen bonding of the carboxyl group, or has a functional group that reacts with the carboxyl group. It has the disadvantage of poor compatibility with compounds.
  • this thermosetting composition is used as a top coat, there is a problem that it is difficult to form a so-called high solid state with a small discharge amount of an organic solvent, or the finished appearance is inferior.
  • this method uses a high temperature of about 170 to 200 ° C for the thermal decomposition of t-butyl group ⁇ , and is a method that can always be sufficiently satisfied from the viewpoint of g-source and energy saving. I can't say. Furthermore, there is a problem that defoaming marks are left on the surface of the cured product due to foaming of isobutene gas, which is a decomposition reaction product, and it cannot be said that this method is necessarily satisfactory.
  • thermosetting composition having excellent stain resistance, stain removal properties, weather resistance (light), and excellent gloss, appearance, water resistance, chemical resistance, environmental preservation, and safety. Creation was desired.
  • the mainstream of stain-resistant paints that have been used in the past are those containing a fluorine-containing resin as the main component.
  • the stain resistance is due to the high weather resistance and water repellency of the fluorine-containing resin described below. there were.
  • Fluorine atom-carbon atom bond energy is greater than hydrogen atom-carbon atom bond energy
  • the atomic radius of fluorine atoms is larger than that of hydrogen atoms, and the polarizability between fluorine molecules is lower than that of (0.68 X 1 0 "2 4 cc) for water repellency due to the surface free energy is low, expressing its function by oil repellency.
  • thermosetting compositions that provide coating performance with excellent stain resistance, stain removal properties, and weather resistance (light) are still in fact found and released.
  • the present invention provides a cured liquid having a good storage resistance at a relatively low temperature, which is excellent in weather resistance, chemical performance, physical performance, particularly, contamination resistance, stain removal property, etc., and has good storage stability.
  • the purpose of the present invention is to provide a thermosetting composition that can be used as a mold.
  • Another object of the present invention is to provide a paint finishing method capable of giving an excellent finish appearance with a small amount of organic solvent discharged, and a coated product obtained by the method. .
  • thermosetting composition having the above preferable properties.
  • An essential component is a dispersion of at least one inorganic oxide sol selected from sols, and is sometimes used
  • thermosetting composition containing a heat-latent acid catalyst that exhibits activity during heat curing can achieve its purpose, and ( ⁇ ) 3 ⁇ 4? 1 self-blocking in one molecule
  • a self-building compound having at least one carboxyl group, at least one reactive functional group capable of forming a chemical bond with the blocked carboxyl group upon heating, and the above-mentioned component (C) as an essential component
  • thermosetting composition comprising the component ( ⁇ ) and the component (d) or the component ( ⁇ ) optionally used and optionally the component (D) can achieve the object, Based on these findings, the present invention was completed. Disclosure of the invention
  • the present invention provides a thermosetting composition characterized by containing ( ⁇ ) a resin component, ( ⁇ ) a curing agent component, and (C) a dispersion of an inorganic sol. Further, the present invention relates to (A) a compound represented by the general formula (1) R 1
  • R ′, R 2 and R 3 are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R 4 is an organic group having 1 to 18 carbon atoms, and R 3 and R 4 are bonded to each other. May form a heterocyclic ring having Y ′ as a hetero atom, and Y ′ is an oxygen atom or a zeo atom.
  • B 1 A compound having two or more reactive functional groups capable of forming a chemical bond with the functional group in the molecule; and
  • C aluminum oxide sol, gay oxide sol, zirconium oxide sol, and antimony oxide sol.
  • a dispersion of at least one selected inorganic oxide sol is an essential component and is optionally used.
  • D Thermosetting characterized by containing a heat-latent acid catalyst that is active during heat-curing. This is a composition having a hydrophilic composition.
  • R 5 , R 6 and R 7 are each a hydrogen atom or an organic group having 1 to 18 carbon atoms
  • R 8 is an organic group having 1 to 18 carbon atoms
  • R 7 and R 8 are bonded to each other. May form a heterocyclic ring having Y z as a hetero atom, wherein ⁇ 2 is an oxygen atom or an ⁇ atom.
  • at least one functional group represented by Self-crosslinking compound having at least one reactive functional group capable of forming a chemical bond with (C) aluminum oxide sol, gay oxide sol, zirconium oxide sol, and antimony oxide sol
  • a dispersion of at least one kind of inorganic oxide sol is an essential component, and in some cases (A) a molecule represented by the general formula (1)
  • R 1 a molecule represented by the general formula (1)
  • R in the formula ', R 2 and R 3 are each a hydrogen atom or a carbon number 1 to: organic groups I 8, R 4 is an organic group having 1 to 18 carbon atoms, R 3 and R 4 are each Y 1 may be a heterocyclic ring having Y ′ as a hetero atom, and Y 1 is an oxygen atom or a zeo atom.
  • a compound having two or more functional groups represented by Or (B) two reactive functional groups capable of forming a chemical bond with the functional group represented by the general formula (2) or the functional group represented by the general formula (1) or both in one molecule. It is intended to provide a thermosetting composition characterized by comprising a compound having the above, and optionally (D) a heat-latent acid catalyst having activity during heat curing.
  • the present invention contains the pigment in an amount of from 0 to 300 parts by weight, preferably from 0 to 100 parts by weight, based on 100 parts by weight of the total nonvolatile components (A) and (B) of the above-mentioned curable composition.
  • This is a paint finishing method that specializes in applying premature paint to a workpiece.
  • a colored film-forming composition is applied on a substrate to form a base coat, and then a clear film-forming composition is applied to the base coat to form a transparent top coat.
  • the method of coating a composite film on an object to be coated comprising: coating only the top coat clear film-forming composition; or any of the top coat clear film-forming composition and the colored film forming composition.
  • a paint finishing method is characterized in that the paint contains any one of the above-described curable compositions.
  • the present invention provides a method in which a colored base coat paint is coated on a base material, a clear coat paint is applied in an unframed state, and after baking, the over clear coat paint is further applied.
  • the clearcoat paint is an acrylic resin aminoplast resin paint
  • the overclearcoat paint is a paint containing any of the above-mentioned thermosetting and durable compositions. Characterized by It provides a paint finishing method.
  • the present invention relates to a coated article obtained by the above-mentioned coating finishing method.
  • thermosetting composition of the present invention examples of the resin component used as the component (A) include a blocked polycarboxyl compound, an acryl polyol resin, a polyester polyol resin, and a fluororesin (described in (1) of the background art). Fluorine resin is also included).
  • various curing agents can be used as the curing agent component used as the component (B).
  • the component (B) may be a fluorine-containing compound.
  • the component (B) may be chemically bonded to the component (A), and the conjugate is a self-like compound.
  • thermosetting composition of the present invention examples of the dispersion of the inorganic sol used as the component (C) include a dispersion of an inorganic oxide sol.
  • the dispersion of the inorganic sol preferably has an average particle size of 100 nm or less, particularly preferably 50 nm or less.
  • the lower limit of the average particle diameter is not particularly limited as long as the inorganic oxide sol can be formed, but is preferably 5 nm or more.
  • the mixing ratio of the above-mentioned component (A) and the above-mentioned component (B) is arbitrarily selected within a range in which a cured product can be obtained, but usually the equivalent ratio is 0.2: 2.0 to 2.0: 2.0. 2, preferably 0.6 to 1.6.
  • the compounding ratio of the component (C) is preferably 0.1 to 60% by weight i% with respect to the total non-volatile content of the component (A) and the component (B).
  • the content is more preferably 0% by weight, and particularly preferably 3 to 40% by weight.
  • thermosetting composition of the present invention the compound used as the component (A) is represented by the general formula (1): R 1
  • R ′, R 2 and R 3 are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, is an organic group having 1 to 18 carbon atoms, and R 3 and R 4 are bonded to each other. May form a heterocyclic ring having Y ′ as a hetero atom, and Y 1 is an oxygen atom or an iodine atom.
  • 2 or more, preferably 2 to 50 functional groups represented by one molecule The compound contained therein is used, and the functional group represented by the general formula (1) is a carboxyl group and a general formula (3)
  • a vinyl ether compound or a vinyl thioether compound represented by It can be easily formed by a reaction with a heterocyclic compound having a vinyl-type double bond as an atom.
  • R 'in the formula (1) and (3), R 2 and R 3 are each a hydrogen atom or an alkyl group having a carbon number of 1-18, Ariru group, an organic group such as an alkaryl group, R 4 is the number of carbon atoms An organic group such as an alkyl group, aryl group, or alkaryl group of 1 to 18; these organic groups may have a suitable substituent; and R 3 and R 4 are bonded to each other.
  • a heterocyclic ring having no or a substituent having Y ′ as a hetero atom may be formed.
  • R ′, R 2 and R 3 include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and an alkaryl group
  • preferred examples of R 4 include a carbon atom having 1 to 10 carbon atoms.
  • Suitable specific examples of the above alkyl group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-hexyl, 2-ethyl Hexyl, 3-methylheptyl, n -nonyl, methyloctyl, methylheptyl, n-decyl, n-ndesinole, n-totesinole, n-tetradecinole, n-heptanesdenole, n-sectactinole group, and the like.
  • the alkyl group includes a cycloalkyl group such as a cyclobutyl group and a cyclohexyl group.
  • Preferred alkyl groups are alkyl groups having 1 to 10 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl , Neopentyl, tert-pentyl, 2-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, 2-ethylhexyl, 3 — Methylheptyl, n-nonyl, methyloctyl, ethylheptyl, n-decyl and cycl
  • the alkyl group also includes an aralkyl group. Suitable examples thereof include benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, and 11- (4-methylphenyl). ) Ethyl, 2- (4-methylphenyl) ethyl, 2-methylbenzyl, and the like.
  • aryl groups and aryl groups include aryl groups such as phenyl, trinole, xylyl, and naphthyl; 4-methylphenyl, 3,4-dimethylphenyl, 3,4,5- Trimethylphenyl, 2-ethylphenyl, n-butylphenyl, tert-butylphenyl, amylphenyl, hexylphenyl, nonylphenyl, 2-tert-butyl-5-methylphenyl, cyclohexylphenyl, cresyl, oxshetylcresyl , 2-methyl-4 tert-butylphenyl, dodecylphenyl, etc., and the like, and preferably ⁇ a number of 6 to 10 phenyl, tolyl, xylyl, 4-methylphenyl, 3,4-dimethylphenyl, 3,4 , 5-trimethylphenyl, 2-ethyl, 2-eth
  • the compound represented by the general formula (3) include, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cycloalkyl Aliphatic vinyl ether compounds such as hexyl vinyl ether and the corresponding aliphatic vinyl thioether compounds, as well as 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-1 2H-pyran , 3,4-Dihydro 2H-pyran, 3,4-Dihydro 2-methyoxy 2H-pyran, 3,4-Dihydro 4,4,4-Dimethyl 2H-pyran 1-one, 3 , 4-Dihidro 2 —Ethokin-1 2 H—Pyran, 3,4—Dihidro 2 H-Pyran—Sodium 2-carboxylate
  • the compound of the component (A) is used for the reaction of a compound having two or more, preferably 2 to 50, carboxyl groups in one molecule with a compound represented by the general formula (3). You can get it.
  • Compounds having two or more carboxyl groups in one molecule include, for example, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, phthalenoic acid, isophthalic acid, and terephthalic acid
  • Aromatic polycarboxylic acids such as aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid
  • two lipoxyl groups in one molecule examples thereof include the above-mentioned polyester resins, acryl resins, maleated polybutadiene resins, and fluororesins having a poly
  • the compound having two or more carboxyl groups in one molecule is, for example, (1) a half ester of a polyol having two or more hydroxyl groups, preferably two to 50 hydroxyl groups per molecule and an acid anhydride.
  • Carboxy group-containing polyisocyanate compound having 2 or more, preferably 2 to 50 isocyanate groups per molecule, and hydroxycarboxylic acid or amino acid are added. It can be obtained by a method such as homopolymerization of an a, ⁇ -unsaturated monomer or copolymerization with another a, -unsaturated monomer, or (4) synthesis of a carboxyl group-terminated polyester resin.
  • the compound of the component (A) may be a fluorine-containing compound, and two or more fluorine-containing compounds obtained by introducing a fluorine atom into the compound obtained by the method of the above (1) to (4) may be used.
  • Polyols having two or more hydroxyl groups per molecule include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol II, glycerin, sorbitol, neopentyl glycol, 1,8-octanediol, 1,4-cyclohexane Hexandimethanol, 2-methyl-1,3-propanediol, 1,2,6-hexantriol, 1,2,4-butanetriol, trimethylolethane, trimethylolproha.
  • Polyhydric alcohols such as pentaerythritol, quinitol, mannitol, tris-hydroxyxyl isocyanurate and dipentaerythritol; these polyhydric alcohols and 7-butyrolactone and £ -force prolatatone Ring-opened adducts with lactone compounds; alcohols of the polyhydric alcohols with isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate Adduct in excess; said polyhydric alcohol and ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediene Adducts of vinyl alcohol compounds such as tanol divinyl ether in excess
  • the fluorine-containing polyol in which a fluorine atom is introduced into the polyol is, for example, copolymerized with a hydroxyl group-containing vinyl ether and a fluorine-containing a, / S-unsaturated monomer, or in some cases, with these other a, And polyols obtained by copolymerizing / S-unsaturated monomers.
  • vinyl ether having a hydroxyl group examples include, for example, hydroxymethyl vinyl ether, hydroxyshethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, and hydroxyoxy.
  • hydroxy vinyl ethers such as heptyl vinyl ether and hydroxy cyclohexyl vinyl ether are exemplified.
  • ⁇ monounsaturated monomers include, for example, olefins such as ethylene, propylene, butylene, isoprene, chloroprene, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, t-butyl Vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, 4-methyl-11-pentyl vinyl ether, cyclopentyl vinyl ether, phenyl vinyl ether, o--, m--, p-- Vinyl ethers such as ryl vinyl ether, benzyl vinyl ether and phenethyl vinyl ether, and aryl ethers, vinyl nitrate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, Vinyl esters and vinyl esters such as vinyl acrylate, vinyl
  • acid anhydrides to be reacted with these polyols include, for example, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid Acid anhydrides of polyvalent carboxylic acids such as acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid.
  • polyisocyanate compound having two or more isocyanate groups per molecule examples include P-phenylenediisocyanate, biphenyldiisocyanate, tolylenediisocyanate, 3,3 ′ Dimethyl-4,4'-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane-1,1,6-diisocyanate , Methylenebis (phenylisocyanate), lysine methylester diisocyanate, bis (isocyanateethyl) fumarate, isophorone diisocyanate, methylcyclohexyldiisocyanate, 2-isocyanateethyl 1,2,6-diisocyanate Trihexanoate and their bullets and isocyanurates Etc. can be mentioned.
  • Examples of the hydroxycarboxylic acid include lactic acid, cunic acid, hydroxypino, 'phosphoric acid, 12-hydroxystearic acid, and malic acid.
  • Examples of the amino acid include DL-alanine.
  • examples of the carboxyl group-containing ⁇ , / 3-unsaturated monomer include acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, and the like.
  • saturated monomer examples include the same ones as those obtained by themselves, and further include 2,2,2-trifluoromethyl acrylate and 2,2,2-trifluoromethyl methacrylate. Fluorine ⁇ , ⁇ monounsaturated monomers and the like can be mentioned.
  • Carboxyl group-containing ⁇ , ⁇ -unsaturated mono ft-form homopolymer or carboxyl group-containing ⁇ monounsaturated monomer and other a,) S-unsaturated mono! :
  • Fluoropolymers in which fluorine atoms have been introduced into a copolymer with a copolymer include, for example, copolymerized carboxyl group-containing a, / S-unsaturated monomer and fluorinated ⁇ , / S-unsaturated monomer Or a copolymer obtained by copolymerizing these with another a, ⁇ -unsaturated monomer.
  • Examples of the ⁇ , ⁇ -unsaturated monomer containing a carboxyl group, the fluorine-containing ⁇ , / 3-unsaturated monomer, and the other ⁇ , ⁇ -unsaturated monomer include the same as described above.
  • the carboxyl group-terminated polyester resin can be easily formed in accordance with a general polyester resin synthesis method in a polybasic acid excess with respect to a polyhydric alcohol.
  • reaction of the thus obtained compound having two or more carboxyl groups in one molecule with the compound represented by the general formula (3) is usually carried out in the presence of an acid catalyst at room temperature to 100 ° C. Performed at a range of temperatures.
  • the compound of the component (A) may be obtained by homopolymerizing a reaction product of a carboxyl group-containing ⁇ ,; 3-unsaturated monomer and a compound represented by the general formula (3) or using other ⁇ , ⁇ -It can also be obtained by copolymerizing with an unsaturated mono-isomer.
  • carboxyl group-containing ⁇ , ⁇ -unsaturated monomer examples include acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, etc., and other ⁇ , 3-unsaturated monomers.
  • Examples of the monomer include methyl acrylate, ethyl acrylate, ⁇ -p-pyracrylate, isopropyl acrylate, ⁇ -butyl acrylate, isobutyl acrylate, sec-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, Cyclohexyl methacrylate , 2-ethylhexyl methacrylate, stearyl methacrylate, styrene, namethylstyrene, p-vinyltoluene, acrylonitrile, etc., and 2,2,2-trifluoromethyl acrylate And
  • thermosetting composition of the present invention the compound of the component (II) may be used alone or in combination of two or more.
  • the compound used as the component ( ⁇ ) When the blocked functional group represented by the general formula (1) in the compound of the component (A) regenerates a free carboxyl group by heating, it reacts with the carboxyl group to form a chemical bond.
  • Those having two or more functional groups, preferably 2 to 50, in one molecule are used.
  • the reactive functional group is not particularly limited as long as it has the above-mentioned properties. Examples thereof include an epoxy group, an oxazoline group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, an isocyanate group, and a bromine group.
  • Preferable examples include an alkylated isocyanate group, a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetate group, and a ketal group.
  • One of these reactive functional groups may be contained, or two or more of them may be contained.
  • conjugate of component (B) examples include bisphenol-type epoxy resins, fl cyclic epoxy resins, glycidyl acrylate, glycidyl methacrylate, and 3,4-epoxycyclohexylmethyl.
  • Homopolymer or copolymer such as acrylate, 3,4-epoxycyclyl hexylmethyl methacrylate, copolymer of glycidylaryl ether with vinylidene fluoride and vinyl ether, polycarboxylic acid or polyol and polyester Polyglycidyl compounds and epoxy group-containing silicone oils obtained by reaction with piclorhydrin, for example, KF-101, KF-103, KF-105, X-22-169AS (trade names, Shin-Etsu Chemical Co., Ltd.
  • Bis (2-year-old azozoline) compounds such as (5-methyl-2-year-old azozoline), hydroxyalkyl-12-year-old azozoline and polyvalent oxazoline compounds obtained by reacting the above-mentioned polyisocyanate compound; —Vinyl—2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2 1-year-old xazoline, 2-isopropenyl—2-year-old xazoline, 2-isopropenyl-1--4-methyl-2-oxazoline
  • Oxazoline group-containing compounds such as homopolymers or copolymers, such as, 2-isopropenyl-5-ethyl-2-oxazoline, and commercially available oxazoline group-containing compounds, such as CX-RS — 1 200, CX-RS-3200 (all manufactured by Nippon Shokubai Co., Ltd.), general formula (4)
  • R e and R 1 are an alkyl group or aryl group having 1 to 18 carbon atoms, respectively, and m is 0, 1 or 2.
  • acryloyloxypropyltrime Homopolymers or copolymers of ⁇ , ⁇ -unsaturated silane compounds such as toxicoxysilane, methacryloyloxypropyltrimethoxysilane, and methacryloyloxypropyltri-n-butoxysilane; and hydrolysis products of these compounds.
  • Silanol group-alkoxysilane group-containing compound aliphatic polyols, phenols, polyalkyleneoxy glycols, 2-hydroxyshethyl acrylate, 2-hydroxyshethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydr Homopolymers of ⁇ .; 5-unsaturated compounds such as roxypropyl methacrylate Is the addition of hydroxy groups such as copolymers and adducts of polyalkanols with these polyols ⁇ !; aliphatic and aromatic diamino and polyamino compounds and the cyanoethylation of the polyols -Containing compounds such as polyamino compounds obtained by reducing the product; imino-group-containing compounds such as aliphatic and aromatic polyimino compounds; ⁇ -fudylenediisocyanate, biphenyldiisocyanate, tolylenediisocyanate 3,3'-
  • Vinyl ether compounds such as copolymers with compounds, and vinyl ether group-vinyl thioether group-containing compounds such as the corresponding vinyl thioether compounds: melamine formaldehyde resin, glycolyl formaldehyde resin, urea formaldehyde resin An aminomethylol group or an alkylated aminomethylol group-containing ⁇ , ⁇ monounsaturated compound, such as a homopolymer or a copolymer of an aminomethylol group or an alkylated aminomethylol group-containing compound; a polyhydric ketone; Polyhydric aldehyde compounds, polyhydric acetal compounds obtained by reacting polyhydric vinyl ether compounds, etc.
  • R 9 and R ′ in the general formula (4) include the same as the specific examples described for R 1 in the general formula (1).
  • a fluorine-containing compound into which a fluorine atom has been introduced can also be used.
  • fluorinated compound of the component (B) examples include ⁇ , -unsaturated unit having the reactive functional group, fluorinated a, ⁇ -unsaturated monomer, and optionally other ⁇ , Copolymers of ⁇ monounsaturated monomers are exemplified.
  • a, yS-unsaturated monomer having a reactive functional group include, for example, ⁇ , having an epoxy group; and 3-unsaturated monomers, for example, P-glycidyloxystyrene, p —Glycidyloxy ⁇ -methylstyrene, ⁇ — (3,4-epoxycyclohexylmethyloxy) styrene, ⁇ — (3,4-epoxycyclohexylmethyloxy) mono- ⁇ -methylstyrene, glycidylethylene, 3, 4-epoxycyclohexylmethylethylene, glycidyl vinyl ether, 3,4-epoxycyclohexylmethylvinyl ether, glycidylaryl ether, 3,4-1 epoxycyclohexylmethylaryl ether, etc.
  • ⁇ ⁇ -unsaturated monomers having the following, for example, vinyltrimethoxysilane and aryltrimethoxysilane Orchid, trimethoxysilyl vinyl ether, trimethoxysilylaryl ether, ⁇ -trimethoxysilylstyrene, ⁇ -trimethoxysilyl-1- ⁇ -methylstyrene, ⁇ -trimethoxysilyloxystyrene, ⁇ -trimethoxysilyloxystyrene ⁇ - / Methylstyrene and the like, and ⁇ , / ⁇ -unsaturated monomers having a hydroxyl group include, for example, hydroxyshethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxycyclohexyl Examples include vinyl ether, hydroxyshetyl aryl ether, hydroxypropyl allyl ether, and hydroxybutyl
  • Examples of ⁇ , —unsaturated mono-isomer having a phthal group include ethylene glycol divinyl ether. 1 Le methanol, ethanol, propanol, Asetaru product of a monohydric alcohol 1 mole, such as butanol, polyethylene glycol divinyl vinyl ether 1 mol of rf Asetaru product with himself monohydric alcohol 1 mole, cyclohexylene Examples include acetalized products of 1 mol of xandimethanol divinyl ether and 1 mol of IHf monohydric alcohol.
  • Examples of the other a, -unsaturated monomers include the same as described above.
  • thermosetting composition of the present invention in addition to the compound having one reactive functional group, a compound having two or more reactive functional groups may be used as the component (II).
  • the component (II) may be used in combination of two or more.
  • a combination in which the respective functional groups are active with each other is not preferable because storage stability is impaired.
  • undesired combinations include, for example, a combination of a functional group selected from an epoxy group, an isocyanate group, a vinyl ether group, a vinyl thioether group, a cyclocarbonate group and a silanol group with an amino group or an imino group, and an isocyanate group.
  • a combination of a vinyl ether group and a hydroxyl group in addition to the compound having one reactive functional group.
  • the ceramic component of the component (C) is at least one selected from a dispersion of a sol of an inorganic oxide of aluminum oxide, gay oxide, zirconium oxide and antimony oxide. Dispersions of various inorganic oxide sols are used. Preferred of these inorganic oxide sols are oxidized silicon oxide sols.
  • these inorganic oxide sols are often supplied as an aqueous dispersion.
  • an aqueous dispersion if the coating composition is aqueous, it can be used as it is.
  • a method of converting ⁇ into a desired organic solvent can be used.
  • Preferred organic solvents to be used are ketone solvents such as methyl isobutyl ketone and cyclohexanone.
  • phase conversion for example, a method of adding a water-soluble organic solvent to an aqueous dispersion and repeating the operation of distilling off water to convert the phase into a desired organic solvent may be used.
  • a method of adding a water-soluble organic solvent to an aqueous dispersion and repeating the operation of distilling off water to convert the phase into a desired organic solvent may be used.
  • the dispersion of the gay oxide sol can be obtained by a method such as adding a gay tetrahalide to water or adding an acid to an aqueous sodium gayate solution.
  • Commercially available products include, for example, water-based dispersions such as Snowtex-1 [product name, manufactured by Nissan Chemical Industry Co., Ltd.] and Snowtex-1 [product name, manufactured by Nissan Chemical Industry Co., Ltd.] Organic Examples of the solvent dispersion include Snowtex MIBK-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.) and Snowtex MIBK-SZ (trade name, manufactured by Nissan Chemical Co., Ltd.).
  • the dispersion of the inorganic oxide sol is preferably subjected to a surface treatment with a silane coupling agent, and particularly preferably the dispersion of a silicon oxide sol is subjected to a surface treatment with a silane coupling agent. Since the dispersion of the surface-treated inorganic oxide sol can introduce various functional groups into the particle surface, when used in the coating composition of the present invention, the resin or the polyisocyanate compound or It becomes easy to chemically bond with organic components such as aminoplast resin. In this way, when the ceramic component and the organic component are chemically bonded, the coating of the film becomes stronger than when the chemical component is not chemically bonded, and the stain resistance, stain removal property, weather resistance, etc. Is improved.
  • silane coupling agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, 7 -methacryloyloxypropyltrimethoxysilane, a-glycidoxypropyltrimethoxysilane, 7-aminopropyltrimethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane.
  • methyl trimethoxy silane, dimethyl dimethoxy silane, 7-glycidoxy propyl trimethoxy silane, 7-methacryloyl oxy propyl trimethoxy silane is preferable, and methyl trimethoxy silane is particularly preferable. It is dimethyldimethoxysilane. Examples of commercially available products include A-162, A-163, and AZ-612 (all trade names, manufactured by Nippon Tunicer Co., Ltd.). These silane coupling agents can be used alone or in combination of two or more. When the surface is treated with a silane coupling agent, the amount of the silane coupling agent is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the nonvolatile content of the inorganic oxide sol.
  • water contained in the aqueous inorganic oxide sol may be azeotropically distilled and dehydrated with an azeotropic solvent with water, and then the inorganic oxide sol may be used. It is preferable to use a dispersion of an azeotropic solvent-dispersed inorganic oxide sol obtained by subjecting the dispersion of the above to surface treatment with a silane coupling agent.
  • the dispersion of the inorganic oxide sol is preferably a dispersion of the oxidized silicon sol.
  • This manufacturing method The dispersion of the inorganic oxide sol obtained in (1) improves stain resistance, stain removal properties, weather resistance, etc., and also enables the concentration of the inorganic oxide sol to be increased. Highly nonvolatile and easy to differentiate. Therefore, there is a wide range of choices for thinner for viscosity adjustment at the time of coating, and it is possible to make the coating film thick.
  • azeotropic solvent examples include water-soluble alcohols, carboxylic esters, and cyclic ethers.
  • water-soluble alcohols include ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, methylcellosolve, ethylcellosolve, and ethylene glycol.
  • Examples of the soluble carboxylate include methyl ftate and ethyl ftate.
  • Examples of the water-soluble cyclic ether include 1,4-dioxane.
  • azeotropic solvents can be used alone or in combination of two or more.
  • a solvent that is immiscible with water may be used for the purpose of increasing the azeotropic distillation dewatering efficiency by using a solvent that is miscible with water.
  • the solvent include benzene, xylene, toluene, cyclohexanone, difuunyl ether, dibutyl ether and the like. These solvents can be used alone or in combination of 2a ⁇ .
  • the amount of force used is limited to a range in which the sol is not agglomerated, and varies depending on the solvent, but is usually preferably in the range of 1 to 10% by weight.
  • the azeotropic distillation dehydration is preferably performed while the azeotropic solvent is being used.
  • the azeotropic distillation dehydration is preferably carried out in the range of from 30 to 100, particularly preferably in the range of from 40 to 80.
  • the azeotropic distillation dehydration can be performed under reduced pressure or normal pressure. Is preferred.
  • the water content in the azeotropic solvent-dispersed inorganic oxide sol after azeotropic distillation dehydration is usually preferably 2% by weight or less, particularly preferably 1% by weight or less.
  • the concentration of the dispersion of the azeotropic solvent-dispersed inorganic oxide sol after the azeotropic distillation and dehydration is preferably such that the heating residue is 55% by weight or less, particularly preferably 25 to 55% by weight. .
  • the surface treatment with a silane coupling agent can be performed by mixing a silane coupling agent with a dispersion of an azeotropic solvent-dispersed inorganic oxide sol after azeotropic distillation and dehydration.
  • the surface treatment temperature with the silane coupling agent is not particularly limited, but is usually preferably in the range of 20 to 100, more preferably in the range of 30 to 90, and particularly preferably 40 to 90. It is preferable to carry out in the range of ⁇ 80.
  • the water content of the solvent-dispersed inorganic oxide sol after the surface treatment with the silane coupling agent is usually preferably 1% by weight or less, particularly preferably 0.5% by weight or less.
  • azeotropic solvent-dispersed inorganic oxide sol can be replaced with a desired solvent as required.
  • Examples of the solvent that can be used for this solvent replacement include the above-mentioned alcohol, acetate, methylethylketone, methylisobutylketone, cyclohexanone, dimethylacetamide, and dimethylformamide.
  • Solvent replacement is preferably performed in the range of 30 to 120, and particularly preferably in the range of 40 to 110, although it depends on the type of solvent used in the replacement.
  • the dispersion of the inorganic oxide sol preferably has an average particle size of 100 nm or less, particularly preferably an average particle size of 50 nm or less.
  • the lower limit of the average particle size is not particularly limited as long as an inorganic oxide sol can be formed, but is preferably 5 nm or more. If the average particle size is larger than 100 nm, the transparency of the clear film is impaired, and the stain resistance and stain removal of the coating film may be reduced.
  • the dispersion of the inorganic oxide sol of the component (C) may be used alone or in combination of two or more.
  • the non-volatile content of the dispersion of the inorganic oxide sol is the total non-volatile content of the component (A) and the component (B), or the component (E), and optionally the component (A)
  • Component (B) is selected to be 0.1 to 60% by weight based on the total non-volatile content of the component. If the non-volatile content of the dispersion of the inorganic oxide sol is less than 0.1% by weight based on the total non-volatile content, the effect of the addition of the dispersion of the inorganic oxide sol will not be sufficiently exhibited, and the coating film will be resistant to contamination. The effect of improving the properties, stain removal properties and weather resistance is not so noticeable, and if it exceeds 60% by weight, the flexibility of the coating film tends to decrease.
  • the non-volatile content of the inorganic oxide sol dispersion is 1 to 40% by weight of the total non-volatile content. A range is preferred.
  • thermosetting composition of the present invention may contain the compound of the component (A), the compound of the component (B), and a dispersion of the inorganic oxide sol of the component (C).
  • a self-crosslinking type compound as an essential component may contain a compound of the above-mentioned component (ii), a compound of the component (ii) or (ii), and / or a compound of the component (D), which are optionally used.
  • the reactive functional group of the component ( ⁇ ) forms a chemical bond with the functional group represented by the general formula (2) and / or the functional group represented by the general formula (1) by heating. .
  • the functional group represented by the general formula (2) in the compound (ii) in the compound of the component (II) includes the functional group represented by the general formula (1), that is, the functional group represented by the general formula (1).
  • the same ones as exemplified can be mentioned.
  • (mouth) reaction Examples of the reactive functional group include the same as those exemplified as the reactive functional group in the compound of the component (B).
  • the compound of the component (E) has one or more carboxyl groups per molecule, preferably
  • a compound having 1 to 50 and the reactive functional group of 1 or more, preferably 1 to 50 is used as a starting material, and is manufactured by the same method as described in the method of manufacturing the compound of the fli component (A). Alternatively, it can be produced by copolymerizing an unsaturated compound having a functional group represented by the general formula (2) and the unsaturated compound having a reactive functional group. .
  • the compound of the component (E) may contain the reactive functional group on the substrate together with the functional group represented by the general formula (2). In this case, the compound (B) Like the component compounds, a combination in which the respective functional groups are mutually active is not preferred because storage stability is impaired.
  • the component (A) and / or the component (B), the component (E), and the component (A) and / or the component (B) optionally used are selected from the components. It is preferable that at least one of the above is a polymer of a monounsaturated compound or a polyester resin, and the above-mentioned general formula (1) or
  • Each component is set so that the equivalent ratio of the functional group represented by (2) to the reactive functional group capable of forming a chemical bond with the functional group is from 0.2: 1.0 to 1.0: 0.2. It is desirable to contain
  • the functional groups represented by the general formulas (1) and (2) of the component ( ⁇ ) and the component ( ⁇ ) regenerate a free carboxyl group under heating
  • Addition reaction may occur to the reactive functional group of the component. In this case, since no de-entanglement reaction occurs during the cross-linking reaction, it can contribute to the reduction of volatile organic substance emissions.
  • thermosetting compositions may optionally maintain good long-term storage stability of the composition, and when cured at a low temperature in a short time, promote a curing reaction
  • a component (D) may optionally contain a heat-latent acid catalyst that is active during heat curing. Wear.
  • the heat latent acid catalyst is preferably a compound exhibiting acid catalyst activity at a temperature of 60 or more. If the heat-latent acid catalyst exhibits an acid catalyst activity at a temperature of less than 60, the resulting composition may cause undesirable situations such as thickening or gelling during storage.
  • Examples of the component (D) as a heat-latent acid catalyst include a compound obtained by neutralizing Brenstead acid or Lewis acid with a Lewis base, a mixture of Lewis acid and trialkyl phosphate, sulfonic acid esters, phosphate esters, onium compounds, And (i) a compound containing an epoxy group; (ii) a compound containing an io-containing compound and (iii) a Lewis acid as an essential component, and optionally (iv) a compound comprising a carboxylic acid compound and / or a carboxylic anhydride compound. .
  • Examples of the compound obtained by neutralizing the Brenstead acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphate esters, boric acid mono- and diesters, and the like.
  • Ammonia monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine and other amines or trialkylamines , Triaryl phosphine, trialkyl phosphite, a compound neutralized with triaryl phosphite, and a nail polish commercially available as an acid monobasic blocking catalyst.
  • 1 0, 3 5 2 5, 5 2 2 5 (Product name, King Industry Co., Ltd.).
  • the compound obtained by neutralizing a Lewis acid with a Lewis base for example BF 3, F e C 1 3 , and S n C, the Lewis acid, such as A 1 C 1 3, Z n C 1 2 ⁇ of himself Lewis Compounds neutralized with a base are mentioned.
  • a mixture of the above-mentioned Lewis acid and a trialkyl phosphite may also be used.
  • Examples of the sulfonic acid ester include a compound represented by the following general formula (5)
  • R ′ is a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group or an alkyl group
  • R ′ 2 is a carbon atom 3 bonded to a sulfonyoxy group via a primary or secondary carbon.
  • alkyl alkenyl, aryl, alkaryl, alkanol, saturated or unsaturated cycloalkyl or hydroxyalkyl
  • Sulfonic acids such as ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid
  • first sulfonic acids such as n-propanol, n-butanol, n-hexanol, and n-octanol Alcohols or isopropanol, 2-butanol, 2-hexanol, 2-octanol,
  • To ester of secondary alcohols such as hexanol, and the like 3-hydroxycarboxylic alkyl sulfonic acid Esuteru compound obtained by the reaction of the Raniwa e sulfonic acids and Okishiran
  • ester phosphates for example, the general formula (6)
  • R 13 represents an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group, and ml represents 1 or 2. More specifically, n-propanol, Primary alcohols such as n-butanol, n-hexanol, n-hexanol, 2-ethylhexanol, and isopropanol, 2-butanol, 2-hexanol, 2-octanol, and cyclohexanol! ⁇ Phosphoric acid monoesters or phosphoric acid diesters of alcohols are listed.
  • Examples of the onium compound include compounds represented by general formulas (7) to (10):
  • R ′ 4 is an alkyl group having 1 to 12 carbon atoms, alkenyl group, aryl group, PT JP96 02971
  • R 15 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, and X is S b F 6 —, As F 6 —, PF 6 or BF. 4 , etc.).
  • Lewis acid as an essential component, and in some cases (iv) suitable for a heat-latent acid catalyst comprising a carboxylic acid compound and a carboxylic acid anhydride compound, and (i) an epoxy group-containing compound.
  • propylene oxide particularly preferred are propylene oxide, butylene oxide, Sansociza E-430 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and Sansocizer E-600 (trade name, new Nippon Rika Co., Ltd.), Guatemala Resin E-8 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), cyclohexenoxide, celoxide 300 (trade name, manufactured by Daicel Chemical Industries, Ltd.), Methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, Cardiura E-10 (trade name, manufactured by Shell) and the like.
  • Glycidyl acrylate, glycidyl methacrylate, aryl glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate homopolymer or other monomer are particularly preferred.
  • the epoxy content thereof is preferably in the range of 0.1 to 7 mol Z kg, particularly preferably in the range of 0.35 to 5 mol kg.
  • the compound containing an epoxy group may be used alone or in combination of two or more.
  • Suitable specific examples of the (ii) zeo containing compound used in the heat latent acid catalyst include, for example, dimethyl sulfide, getyl sulfide, di-n-propyl sulfide, di-n-butyl sulfide, di-n- Alkyl sulfides such as hexyl sulfide, diisopropyl pyrsulfide, g-sec-butyl sulfide, g-tert-butyl sulfide, g-n-butyl sulfide, g-2-ethylhexyl sulfide, and 2- (ethylthio) ethanol , 2,2'-Hydroxyalkyl sulfides and derivatives thereof, such as thiophenol, bis (2-methoxethyl) sulfide, and derivatives containing aromatic rings such as diphenyl sulfide and thio
  • di-n-propyl sulfide di-n-butyl sulfide, di-n-hexyl sulfide, diisopropyl sulfide, di-sec-butyl sulfide, and di-tert- Alkyl sulfides such as butyl sulfide, di-n-octyl sulfide, and di-2-ethylhexyl sulfide; 2- (ethylthio) ethanol, bis (2-methoxethyl) sulfide, methyl methylthio ftate, methyl ethyl thiopropionate , Tetrahydrotifen and 1,4-year-old Xathian.
  • the (ii) -containing compound may be used alone or in a combination of two or more.
  • Suitable specific examples of the (iii) Lewis acid used for the heat latent acid catalyst include, for example, boron trifluoride, aluminum trichloride, titanium (II) chloride, titanium (II) chloride, ferrous chloride, and chloride Gold halides such as ibM lead, odorous lead, stannous chloride, stannic chloride, stannous bromide, stannic bromide, trialkylboron, trialkylaluminum, dialkyl Organic metal compounds such as aluminum halides, monoalkylaluminum halides, and tetraalkyltins, aluminum diisopropoxyshetyl acetate, aluminum tris (ethyl acetate) aluminum, isopropoxybis (ethyl acetate) aluminum Aluminum, triacetate acetate, bis (ethyl acetate acetate) n-Propyl acetoacetate Aluminum, Tris (n-butyl acetoacetate) Aluminum, Mono
  • chelates of boron, aluminum, tin, titanium, zinc and zirconium, gold ash, and halides preferred are chelates of boron, aluminum, tin, titanium, zinc and zirconium, gold ash, and halides.
  • carboxylic oxide compound and a carboxylic acid compound or a carboxylic acid anhydride compound are not used, from the viewpoint of solubility in an organic solvent, the chelating compounds of boron, aluminum, tin, titanium, zinc, and zirconium, and gold silicate are particularly preferred. Preferred are mentioned.
  • the (iii) Lewis acid may be used alone or in combination of two or more.
  • Suitable specific examples of (iv) the carboxylic acid compound used for the heat latent acid catalyst include formic acid, acetic acid, propionic acid, severe acid, 2-ethylhexyl acid, lauric acid, stearic acid, oleic acid, Monovalent carboxylic compounds such as linoleic acid, linolenic acid, atarilic acid, methacrylic acid, monochloroacetic acid, dichloroacetic acid, and trichloroic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid Polycarboxylic compounds such as acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalenoic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, itaconic acid, mesaconic acid, and fumaric acid , And carboxyl
  • a monovalent or polyvalent carboxylic acid compound having a relatively low molecular weight is preferable, and a monovalent or polyvalent carboxylic acid compound having a molecular weight of 300 or less is particularly preferable.
  • Suitable specific examples of the carboxylic anhydride compound used in the heat latent acid catalyst Acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, lauric anhydride, oleic anhydride, linoleic anhydride, stearic anhydride, linolenic anhydride, anhydrous succinic acid, phthalic anhydride, maleic anhydride Acid, trimellitic anhydride, pyromellitic anhydride, isovaleric anhydride, n-butyric anhydride, n-butyric anhydride, n-butyric acid, n-butyric acid anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride , Lipic anhydride, lendic anhydride, palmitic anhydride, myristic anhydride, tetrapropenyl succinic anhydride, tetrahydrophthalic
  • acid I anhydride particularly preferred are acid I anhydride, propionic anhydride, butyric anhydride, isocyanic anhydride, radiic anhydride, oleic anhydride, stearic anhydride, n-hydroproic acid, and n-hydroproic anhydride.
  • acid I anhydride propionic anhydride, butyric anhydride, isocyanic anhydride, radiic anhydride, oleic anhydride, stearic anhydride, n-hydroproic acid, and n-hydroproic anhydride.
  • examples include capric prillic acid, n-capric anhydride, palmitic anhydride, myristic anhydride, trichloroacetic anhydride, dichloroacetic acid anhydride, monochloroacetic anhydride, trifluoroacetic anhydride, and heptafluorobutyric anhydride.
  • the effect of (iv) the carboxylic acid compound and the carboxylic anhydride compound on the solubility in an organic solvent is remarkable when the Lewis acid is a gold halide.
  • the (iv) carboxylic acid compound and carboxylic anhydride compound may be used alone or in combination of two or more.
  • the mixing ratio of each component at the time of producing the thermal latent acid catalyst is not particularly limited, but (iii) relative to the atoms of boron, aluminum, tin, lead, or a transition element of the component Lewis acid.
  • the apposition ratio of the epoxy group of the compound containing an epoxy group (i) and the i-atom of the i-containing compound (ii) is preferably in the range of 0.2 to 10; Each is preferably in the range of 0.5 to 5. If the equivalent ratio is less than 0.2, the activity of the Lewis acid during storage may not be sufficiently suppressed. If the equivalent ratio exceeds 10, the acid catalyst activity during heating will increase. It may be difficult to show the properties.
  • the equivalent ratio of the acid anhydride group of the anhydrous sulfonic acid compound is not particularly limited, but is preferably in the range of 0.05 to 10 and particularly preferably in the range of 0.1 to 5 If the equivalent ratio is less than 0.05, the solubility of the latent heat acid catalyst in an organic solvent may be insufficient. If it exceeds 0, the activity of the Lewis acid may not be sufficiently suppressed during storage.
  • the heat-latent acid catalyst is prepared by mixing (i) a compound containing an epoxy group, (ii) an iodide-containing compound and (iii) a Lewis acid in any order in the presence or absence of a solvent. By doing so, it can be easily manufactured. Among them, (i) a compound containing an epoxy group and (ii) an io-containing compound are preliminarily mixed, and then (iii) a Lewis acid is mixed, or (ii) an io-containing compound and (iii) a Lewis acid are mixed. And (i) a compound containing an epoxy group and then a compound containing an epoxy group.
  • the mixing order of the carboxylic acid compound and the anhydrous rubonic acid compound can be arbitrarily determined. Among them, (i) a compound containing an epoxy group, (ii) an iodide-containing compound, (iii) a Lewis acid, and (iv) a carboxylic acid compound and / or an anhydrous rubonic acid compound. Is preferred. Further, in the production of the heat-latent acid catalyst, after mixing two, three, and if necessary, four or five components, the mixture is allowed to react at room temperature to 100 to 10 minutes to 100 minutes. Heating for 0 hours may be preferable because the heat-latent reaction of the Lewis acid is further promoted.
  • the solvent used here examples include an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, and a mixed solvent thereof. Further, the amount of the solvent to be used may be determined as appropriate: 1 1, but it is usually preferable that the amount of the heat-latent acid catalyst is 1 to 90% by weight.
  • the heat-latent acid catalyst of the component (D) may be used singly or in combination of two or more.
  • the total non-volatile content of component (A) and component (B), or component (E) and optionally used component (A) and / or component (B) is usually 0.01 to 2 per 100 parts by weight. It is selected so as to be blended in a range of 0 parts by weight, preferably in a range of 0.02 to 10 parts by weight.
  • the amount of the catalyst is too small to sufficiently exert the effect of accelerating the reaction.
  • the amount of the heat-latent acid catalyst exceeds 20 parts by weight, the effect of accelerating the reaction is not improved in terms of the amount, but rather a large amount of the catalyst remains in the thermosetting composition. Is not preferable because the physical properties of the coating film may be deteriorated.
  • the temperature at which the blocked functional group represented by the general formula (1) or (2) regenerates a free carboxyl group the reactive function Curing is completed by heating for 5 seconds to 24 hours, usually in the range of 50 to 300 hours, although it varies depending on the type of group, the type of heat-latent acid catalyst, and the like.
  • the curable composition of the present invention can be used as it is, or as necessary, by blending various additives such as a coloring pigment, a filler, a solvent, an ultraviolet absorber, an antioxidant, and a flow regulator, to prepare a paint or an ink. It can be used for various applications utilizing curability, such as adhesives, agents and molded articles.
  • thermosetting composition of the present invention can be produced by mixing the above components and blending various additives as necessary.
  • the method of blending the components and the method of adding the various additives are not particularly limited, and can be performed by various methods, and the mixing order and the addition order can be performed in various orders.
  • thermosetting composition of the present invention may be used as a paint or the like used in a method for preparing an article having a single-layer top coating or a multilayered coating (composite coating) composed of a colored base coat and a clear top coat. Paints for automobiles, paints for railways' vehicles, paints for pre-coat and post-coat metal products, paints for electrical equipment, paints for steel structures, paints for machinery, paints for building materials, and insulation for electric and electronic parts. It is extremely useful in moisture-proof, fire-proof coatings and other industrial coatings.
  • the (A) resin component and (B) curing agent component of the thermosetting composition The pigment is preferably compounded in an amount of 0 to 300 parts by weight, particularly preferably 0 to 100 parts by weight, based on 100 parts by weight of the total nonvolatile components of the pigment. When a pigment is blended, it is preferable to blend at least 0.1 part by weight.
  • the pigments used are various pigments such as organic pigments and inorganic pigments.
  • organic pigments and inorganic pigments For example, aluminum, copper, brass, bronze, stainless steel, or mica-like iron oxide, scaly, each of which has been subjected to a surface treatment.
  • Metallic powders, and gold pigments such as mica chips coated with titanium oxide or acid are used.
  • inorganic pigments such as titanium dioxide, iron oxide, yellow acid, carbon black, etc.
  • organic pigments such as phthalocyanine blue, phthalocyanine green, and quinacridone red pigment, sedimentable barium sulfate, clay, silica, Extender such as talc;
  • the composite coating film examples include, for example, applying a colored film-forming composition on a substrate to form a base coat film, and then coating the base coat film with the thermosetting composition of the present invention.
  • a composite coating film obtained by a coating finishing method comprising applying a clear film-forming composition as described above to form a transparent top coat film.
  • the colored film-forming composition of the base coat film contains a resin binder and a pigment.
  • the resin binder examples include various binders such as known acryl resin, polyester resin (including alkyd resin), polyurethane resin and melamine resin.
  • At least one kind of commonly used additives such as a surfactant, a repelling agent, a thixotropic agent, an agent, an anti-foaming agent, an organic solvent, and a catalyst is added.
  • a surfactant such as a repellent, a thixotropic agent, an agent, an anti-foaming agent, an organic solvent, and a catalyst is added.
  • the pigment is preferably blended in an amount of 1 to 80% by weight, particularly preferably 3 to 60% by weight.
  • pigments such as organic pigments and inorganic pigments are used.
  • organic pigments and inorganic pigments aluminum, copper, brass, bronze, stainless steel, or mica-like acid, flake-shaped Metallic pigments such as Yurik powder and mica fragments coated with titanium oxide and iron oxide are used.
  • titanium dioxide, iron oxide, yellow examples include inorganic pigments such as color iron oxide and carbon black; organic pigments such as phthalocyanine blue, phthalocyanine green, and quinacridone red pigment; and extender pigments such as precipitated barium sulfate, clay, silica, and talc.
  • the above-mentioned method for finishing the coating of the composite coating film comprises adjusting the color film-forming composition of the base coat film to a desired viscosity by heating according to the temperature or by adding an organic solvent or a reactive agent. After that, the coating film that has been dried using an air spray, an electrostatic air spray, a roll coater, a flow coater, a coating machine using a dive-type coating machine, or a brush, a bar coater, an applicator, or the like is used.
  • the film thickness after drying using the above method is usually 5 to 40 / m, preferably 7 to 40 / m. 3-5, room temperature ⁇ 10
  • the composition is allowed to stand at a temperature of 0 to 10 to 20 minutes, and then the clear film-forming composition of the clear coat film is dried using the above-mentioned method to have a film thickness of 10 to 10: 100 m, preferably 10 to 100 m.
  • the coating method is preferably spray coating among the above methods.
  • a composite coating for example, a colored base coat paint is applied on a base material, a clear coat is applied in an unmounted state, and after baking, it is further overcleared.
  • an acrylic resin Z-aminoplast resin intermediate is used as the clear coating intermediate, and the thermosetting composition of the present invention is used as the overclear coating intermediate.
  • a composite coating film obtained by a paint finishing method comprising the use of a precipitating composition composed of a product.
  • the same coloring base coat paint as that used for the self-composite coating can be used.
  • Acrylic resin aminoplast resin paint is used as the clear coat paint to be applied in an uncrosslinked state on the colored base coat coating film.
  • the acrylic resin include (a) an ester of (meth) acrylic acid of an alkyl alcohol having a number of 1 to 12 and (b) a hydroxy having a polymerizable double bond. And (c) styrene, (e) acrylonitrile, and (f) other monomer (s), as the main components, a monomer having a carboxyl group having a polymerizable double bond, and (c) a monomer having a carboxyl group having a polymerizable double bond. Examples thereof include those obtained by copolymerizing monomers.
  • aminoblast resin examples include, for example, melamine resin and guanamine resin.
  • One of these aminoblast resins may be used, or two or more thereof may be used in combination. More specifically, as long as two or more reactive groups are contained in one molecule, there is no particular restriction.
  • One triazine ring is present in one molecule of melamine or guanamine resin. But you can.
  • the reactive group present in such a resin preferably, a methylol group, an imino group, and those obtained by etherifying a methylol group with methanol / butanol are exemplified.
  • the mixing ratio of the acryl resin and the aminoplast resin is not particularly limited, but the weight ratio of the acryl resin to the aminoblast resin is in the range of 90:10 to 50:50. Are preferred, and particularly preferred is a range of 80:20 to 60:40.
  • a curing catalyst for aminoblast resin may be blended.
  • aminoblast resin curing reaction catalysts include, for example, phosphoric acid-based curing catalysts, sulfonic acid-based curing catalysts such as toluenesulfonic acid and dodecylbenzenesulfonate, and amine block bodies thereof.
  • phosphoric acid-based curing catalysts phosphoric acid-based curing catalysts
  • sulfonic acid-based curing catalysts such as toluenesulfonic acid and dodecylbenzenesulfonate
  • amine block bodies thereof amine block bodies thereof.
  • One of these compounds may be used alone, or two or more of them may be used in combination, and the curing time may be adjusted in combination with another compound.
  • the amount of these compounds added is preferably in the range of 0.01 to 2% by weight of the total nonvolatile components in the acrylic resin aminoplast resin paint.
  • the clear coat paint in the method of finishing the above-mentioned composite coating film may contain additives such as a regulator, a leveling agent, an anti-gelling agent, an antioxidant, an ultraviolet absorber, and a radical scavenger, if desired. Can also be blended.
  • a preferred example of the method of finishing the above-mentioned composite coating film is to obtain a desired viscosity by heating the colored base coat paint as needed or adding an organic solvent or a reactive diluent.
  • a commonly used coating machine such as an air spray, electrostatic air spray, roll coater, flow coater, or dive-in type coating machine, or dry using a brush, bar coater, or applicator.
  • the film is applied so that the film thickness is usually 5 to 40 ⁇ , preferably 7 to 35 zm, and left at room temperature to 100 ° C. for 1 to 20 minutes, and then the clear coat paint is applied as described above. Apply the coating so that the film thickness after drying by the method is 10 to: ⁇ ⁇ ⁇ zm, preferably 10 to 60 zm, and heat harden at a temperature of 50 to 300 for 5 seconds to 24 hours. I'll make you realistic.
  • the over-clear coat paint is applied using the above-mentioned method so that the film thickness of the dried coat is 5 to 50 m, preferably 5 to 20 m, and the temperature is 50 to 300 ". For 5 seconds to 24 hours.
  • a paint can be used in an amount of 0.;! To 60% by weight based on the total non-volatile content of the component ( ⁇ ').
  • This alternative paint is one embodiment of the thermosetting composition of the present invention.
  • acrylic polyol resin as the component ( ⁇ ′) examples include (a) an ester of (meth) acrylic acid of an alkyl alcohol having 1 to 12 carbon atoms, and (b) a hydroxyl group-containing monomer having a polymerizable double bond. And (c) a carboxyl group-containing monomer having a polymerizable double bond as an essential component, and if necessary, (d) styrene, (e) acrylonitrile, and (f) other monomers. Those obtained by copolymerization are exemplified.
  • the (meth) acrylic acid ester of coal (hereinafter referred to as “acrylic ester”) is preferably used in a proportion of 10 to 90% by weight based on the weight of all monomers.
  • Acrylic ester is an essential component for controlling the glass transition temperature of a coating film. If the alkyl group of the alcohol moiety has more than 12 carbon atoms, the glass transition temperature of the resulting resin will increase. It tends to be too low. If the amount of the ester is less than 10% by weight, the glass transition temperature of the obtained resin cannot be raised to 50 or more unless other low polymerizable monomers are used.
  • the weather resistance of the coating film may be significantly reduced.
  • the content exceeds 90% by weight, the required amount of hydroxyl group or carboxyl group cannot be introduced into the resin, and a coating film having high weather resistance, high stain resistance, and high stain removal properties can be obtained. Hateful.
  • the particularly preferred amount of the acryl-based ester is in the range of 35 to 80% by weight.
  • the alkyl alcohol having 1 to 12 carbon atoms forming the acryl-based ester of the component (a) may be any alcohol having a linear, branched, or cyclic alkyl group.
  • acrylic ester of the component (a) examples include, for example, methyl methacrylate, ethyl methacrylate, mono-n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, iso-butyl methacrylate, t-methyl methacrylate Butyl, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, monoethyl methacrylate, 2-ethylhexyl methacrylate, adamantyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acrylate n-Propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pen
  • the hydroxyl group-containing monomer having a polymerizable double bond of the component (b), which is used as an essential monomer component accounts for 10 to 50% by weight based on the weight of all monomers. It is preferable to use them. If the amount is less than 10% by weight, it is difficult to introduce necessary crosslinking points into the obtained resin, and a coating film having high weather resistance, high stain resistance, and high stain removal properties can be obtained. Hateful. On the other hand, if it exceeds 50% by weight, the crosslink density of the coating film becomes too high, or unreacted hydroxyl groups remain in the resin during the bridging reaction between the obtained resin and the component (b).
  • the particularly preferred use i of the monomer of the component (b) is 10 to 30% by weight. .
  • hydroxyl group-containing monomer having a polymerizable double bond for example, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 1,4-butanediol monomethacrylate Acrylates, £ -prolactone adducts of hydroxymethyl methacrylate, ethylene oxide and propylene oxide adducts of hydroxymethyl methacrylate, hydroxyshetyl acrylate, hydroxypropyl ata Relate, hydroxybutyl acrylate, 1,4-butanediol monoatalylate, and hydroquinethyl acrylate And ethylene oxide and propylene oxide adducts. These may be used alone or in combination of two or more.
  • the monomer having a polymerizable double bond and having a polymerizable double bond which is used as an essential monomer component, is 0.1 to 0.1% by weight based on the weight of all monomers. It is preferable to use them together. If the amount is less than 0.1% by weight, the resulting resin will have too low an acid value, and will have disadvantages such as low curability with the aminoblast resin. In addition, the storage stability and pot life of paint tend to be significantly reduced. In view of the storage stability of the paint and the pot life, the more preferable use of the component (c) is; -5% by weight, and particularly preferably 1-3% by weight.
  • styrene as the component (d) is not an essential component, and is used as necessary for the purpose of improving the appearance such as the reflectivity of the coating film.
  • styrene is used, it is preferably used in a proportion of 20% by weight or less based on the total weight of the monomers.
  • the weather resistance, stain resistance, and stain removability of the resulting coating film tend to decrease.
  • the particularly preferred amount when styrene is used is in the range of 1 to 18% by weight.
  • acrylonitrile as the component (e) is not an essential component, and is used as necessary for the purpose of improving the adhesion of the coating film to the substrate, the impact resistance, and the like.
  • acrylonitrile simply! : It is preferably used in a proportion of 20 weight or less based on the total weight of the body. If the amount of acrylonitrile used exceeds 20% by weight, the weather resistance, stain resistance and stain removal of the coating tend to decrease. From the viewpoint of the balance of adhesion of the coating film to the substrate, impact resistance, weather resistance, stain resistance, stain removal property, etc., the particularly preferred amount of acrylonitrile used is 1 to 18 weight. % Range.
  • the other monomer of the component (f) is not an essential component, and is appropriately used as needed in designing a coating film depending on the base material and intended use.
  • it is preferably used in a proportion of 10% by weight or less based on the total weight of the monomers. If the amount used exceeds 10% by weight, it is difficult to obtain a coating film having desired physical properties.
  • Examples of the body include, for example, Phosmer (manufactured by Unichemical), glycidyl methacrylate, glycidyl acrylate, allyl methacrylate, allyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclo Hexylmethyl acrylate, phenyl methacrylate, Phenyl acrylate, na-methylstyrene, p-vinyltoluene, methacrylamide, acrylamide, N, N-dimethylmethacrylamide, N, N-dimethylacrylamide, methacrylic acid 1, 2, 2, 6,6-pentamethyl-4-piperidyl, acrylolic acid-1,2,2,6,6-pentamethyl-14-piperidyl, methacrylic acid-1,2,2,6,6-tetramethyl-1-piperidyl, Acrylic acid 1,2,2.6,6-tetramethyl
  • a fluorine-containing acryl polyol resin obtained by introducing a fluorine atom into the acrylic polyol resin as the component (II) can also be used in the present invention.
  • the fluorinated acrylacryl polyol resin can be obtained by copolymerizing a fluorinated ⁇ , ⁇ -unsaturated monomer in addition to the above-mentioned monomers.
  • the fluorine-containing ⁇ , unsaturated monomer is the same as that of it.
  • a resin of the ( ⁇ ′) component is obtained.
  • the polymerization method at this time is not particularly limited, and a known method such as a solution polymerization, a suspension polymerization, an emulsion polymerization, a bulk polymerization, or a precipitation polymerization in an organic solvent can be used.
  • a known method such as a solution polymerization, a suspension polymerization, an emulsion polymerization, a bulk polymerization, or a precipitation polymerization in an organic solvent can be used.
  • There is no particular limitation on the type of polymerization For example, any of radical polymerization, cationic polymerization, and anion polymerization can be used. Among them, radical polymerization is preferred from the industrial viewpoint.
  • Examples of the polymerization initiator used in the radical polymerization include, for example, t-butyl hydroperoxide, cumene hydropoxide, t- butyl peroxy neodecane, t- butyl peroxyvivalate, and t -hexyloxy.
  • Organic peroxides such as 2-ethylhexanoate and methylethylketone peroxide, or 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azo Examples include azo initiators such as bis (2-methylpropionitrile) (AIBN) and 2,2'-azobis (2-methylbutyronitrile). Of course, it is not limited to these.
  • These radical polymerization initiators may be used alone or in a combination of two or more.
  • the polymerization temperature is preferably in the range of 60 to 150. If the temperature is lower than 60, the radical polymerization initiator is difficult to decompose and the reaction is difficult to proceed. If the temperature is higher than 150, the radical polymerization initiator is decomposed by heat to generate radicals. Even if it is formed, its life is short and the growth reaction does not proceed effectively.
  • the polymerization time depends on the polymerization temperature and other conditions, and cannot be unconditionally determined, but generally about 2 to 6 hours is sufficient.
  • polyester polyol resin examples include those obtained by subjecting a polybasic acid and a polyhydric alcohol to a condensation reaction according to a conventional method.
  • polyester polyol resin examples include aliphatic polycarboxylic acids having 2 to 22 carbon atoms, such as succinic acid, adipic acid, azelaic acid, sebacic acid, and decamethylene dicarboxylic acid, phthalic acid, isophthalic acid, and the like.
  • Aromatic polycarboxylic acids such as terephthalic acid, trimellitic acid, and pyromellitic acid; alicyclic polycarboxylic acids such as tetrahydrophthalic acid and hexahydrophthalic acid; succinic anhydride; maleic anhydride; phthalanoic anhydride; tetrahydro Acid anhydrides such as phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned. These polybasic acids may be used alone or in combination of two or more.
  • polyhydric alcohols examples include ethylene glycol, 1,2- and 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and 1,6-.
  • Xandiol diethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A, glycerin, sorbitol, neopentyl glycol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3 —Propanediol, 1, 2, 6—hexanetriol, 1,2,4—butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, quini Alcohols such as tol, mannitol, tris-hydroxyxetyl isocyanurate, dipentyl erythritol, and polyhydric
  • Adducts below such polyhydric alcohols and ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pentanediol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether Adducts of vinyl ether compounds with alcohols in excess of alcohol, and the polyhydric alcohols and alkoxysilicone compounds, for example, KR-213, KR-217, KR-9218 (all trade names, Shin-Etsu Chemical Co., Ltd.) And condensates in excess of alcohol.
  • One of these polyhydric alcohols may be used, or two or more of them may be used in combination.
  • the resin used as the In-self ( ⁇ ') component preferably has a glass transition temperature in the range of 50 to 120. If the glass transition temperature is less than 50, the resulting coating film has insufficient hardness and it may be difficult to obtain a highly weather-resistant coating. If the glass transition temperature exceeds 120, the P property at the time of mounting may be poor. Along with the deterioration, the resulting coating film may have reduced appearance such as cinematography and luminosity. Further, by adjusting the glass transition temperature to the above range, the low stain removal property, which is a defect of the coating composition proposed in Japanese Patent Application Laid-Open No. 4-173882, is improved.
  • Particularly preferred glass transition temperature is in the range of 50 to 100 in view of the hardness of the coating, appearance, decontamination and workability.
  • the resin preferably has a number average molecular weight in the range of 3,000 to: 100,000.
  • the number average molecular weight is more preferably in the range of 4,000 to 70,000, particularly preferably in the range of 4,500 to 40,000.
  • the hydroxyl value is preferably in the range of 50 to: I 5 OmgKOH / g.
  • the hydroxyl value is less than 5 OmgKOHZg, the resulting coating film Insufficient bridge density makes it difficult to obtain high stain resistance and high stain removal properties. If it exceeds 15 OmgKOHZg, the structure of the coating film becomes too dense and the shrinkage stress during coating film formation becomes large. When it becomes impossible to alleviate the cracks, cracks and the like easily occur in the coating film.
  • the hydroxyl value is particularly preferably in the range of 50 to: I 3 OmgKOHZg from the viewpoints of the stain resistance of the coating film, the stain removal property, and the suppression of crack generation.
  • the acid value is preferably in the range of 1 to 25 mgKOH / g. If the acid value is less than lmgKOHZg, inconveniences such as low curability with aminoplast resin may occur.If the acid value exceeds 2 SmgKOHZg, the storage stability of paint and the pot life will be extremely low. There is a tendency to decrease.
  • the acid value is particularly preferably in the range of 2 to 2 OmgKOHZg from the viewpoints of storage stability and pot life of the paint.
  • Polyisocyanate compound containing two or more isocyanate groups in one molecule, polyblock isocyanate containing two or more block isocyanate groups in one molecule, as a curing agent for ri ( ⁇ ') component One or more compounds selected from compounds and aminoblast resins are used.
  • polyisocyanate compounds include, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenyl methane diisocyanate, xylylene diisocyanate, dicyclohexyl methane-4, Compounds called isocyanate monomers such as 4 'diisocyanate, and polyisocyanate derivatives such as biuret, isocyanurate, and adduct of trimethylolpropane are preferably exemplified.
  • One of these polyisocyanate compounds may be used, or two or more thereof may be used in combination.
  • the polyblock isocyanate compound can be produced, for example, by blocking the above polyisocyanate compound.
  • the blocking agent used for this blocking may be suitable.
  • ketoxime-based blocking agents such as £ -caprolactam, methylethyl ketoxime, methylisoamylketoxime, methylisobutylketoxime, phenol-based blocking agents such as phenol, cresol, catechol, ditrophenol, isopropanol, Trimethi
  • an alcohol-based blocking agent such as roll propane
  • an active methylene-based blocking agent such as malonate and acetate acetate.
  • One type may be used, or two or more types may be used in combination.
  • aminoblast resins include, for example, melamine resins and guanamine resins.
  • One kind of these aminoplast trees may be used, or two or more kinds thereof may be used in combination. More specifically, there are no other restrictions as long as two or more reactive groups are contained in one molecule, and one or more triazine rings are present in one molecule of melamine or guanamine resin. But you can.
  • the reactive group present in these resins preferably includes a methylol group, an imino group, and those obtained by etherifying a methylol group with methanol / butanol or the like.
  • the mixing ratio of the ( ⁇ ') component and the ( ⁇ ') component is such that the ( ⁇ ') component contains one or more polyisocyanate compounds containing two or more isocyanate groups in one molecule, and one or more isocyanate groups.
  • the molar ratio of the isocyanate and the ⁇ or blocked isocyanate group in the component ( ⁇ ') to the hydroxyl group in the component ( ⁇ ') is 0.6. It is preferably in the range of from 1.6 to 1.6, and particularly preferably in the range of from 0.8 to 1.2.
  • this molar ratio is less than 0.6, the hydroxyl group in the resin may remain unreacted during the cross-reaction between the polyisocyanate compound of the B and J components and the resin of the ( ⁇ ') component.
  • the molar ratio exceeds 1.6, on the other hand, when the molar ratio exceeds 1.6, the dissocyanate group and the molybdenum group may be deteriorated.
  • ⁇ or blocked isocyanate groups may remain unreacted, and in this case, the water resistance or moisture resistance of the coating film may be reduced, and the water resistance of the coating film may be deteriorated.
  • the solid content weight ratio of the ( ⁇ ′) component to the ( ⁇ ′) component is preferably in the range of 97/3 to 60/40. , 955-65-35, more preferably in the range of 910-730.
  • Tin compounds include, for example, tin halides such as tin chloride and tin bromide, and organotin compounds such as dibutyltin diacetate and dibutyltin dilaurate.
  • Zinc compounds include, for example, halogens such as zinc chloride and zinc bromide. Examples include zinc salts of organic acids such as zinc oxide, zinc octoate, and zinc laurate.
  • the curing reaction catalyst is preferably used in a proportion of 0.01 to 5% by weight based on the total solids in the coating material containing the inorganic sol.
  • a more preferable compounding ratio of the curing reaction catalyst is in the range of 0.01 to 2% by weight based on the total solids in the composition.
  • One of the tin compound and the zinc compound as the curing reaction catalyst may be used alone, or two or more of them may be used in combination, or may be used in combination with another curing reaction catalyst.
  • a hard iS catalyst of the aminoblast resin may be used.
  • the amino blast resin hardening catalyst include, for example, a phosphoric acid-based curing catalyst, a sulfonic acid-based curing catalyst such as toluenesulfonic acid and dodecylbenzenesulfonic acid, or an amine block thereof.
  • a phosphoric acid-based curing catalyst such as toluenesulfonic acid and dodecylbenzenesulfonic acid
  • One of these compounds may be used alone, or two or more of them may be used in combination, and the curing time may be adjusted in combination with another compound.
  • the amount of addition of these compounds is preferably in the range of 0.01 to 2% by weight based on the total solid content of the filler containing the inorganic sol.
  • the content is less than 0.01% i%, the paint containing inorganic sol hardens and the effect of these compounds may not be exhibited.
  • the performance of the paint film such as water resistance and moisture resistance, may be adversely affected, and the stain resistance, stain removal properties, and weather resistance of the paint film may be reduced.
  • the dispersion of the inorganic oxide sol of the component (C) is the same as the component (C) in the thermosetting composition of the present invention.
  • the dispersion of the inorganic oxide sol of the component (c) is dispersed and stabilized in a polymerization solvent, and then polymerized under the same polymerization conditions as the polymerization of the resin of the component ( ⁇ ′), or After polymerizing the resin of the ( ⁇ ′) component, the dispersion of the inorganic oxide sol is stabilized in the resin solution with or without heating to obtain an inorganic oxide sol dispersion-stabilized resin solution.
  • the alternative paint is prepared by uniformly mixing the resin, if necessary, the resin of the component ( ⁇ ′), the curing agent of the component ( ⁇ ′), and various additives used as required. Can be prepared.
  • the substrate on which the coating composition comprising the thermosetting composition of the present invention or the alternative coating composition is applied is not particularly limited, and various substrates can be used.
  • These 3 ⁇ 4tts may be those which have been subjected to a surface treatment in advance, or those having a coating formed on the surface in advance.
  • Examples of the coated article obtained by applying the fibrinated 3 ⁇ 4a composition of the present invention or the aforementioned alternative composition include: buildings, structures, wood products, metal products, plastic products, rubber products, and processed products. Examples include paper, ceramic products, and glass products. More specifically, automobiles, automotive parts (for example, parts such as bodies, bumpers, boilers, mirrors, wheels, interior materials, etc., of various materials), metal sheets such as steel sheets, Yuen vehicles, motorcycle parts, road materials (for example, guard rails, traffic signs, etc.), tunnel materials (for example, side wall boards), ships, railway vehicles, aircraft, printing equipment, printing equipment parts, furniture, musical instruments , Home products, building materials, containers, office supplies, sporting goods, toys and the like.
  • automotive parts for example, parts such as bodies, bumpers, boilers, mirrors, wheels, interior materials, etc., of various materials
  • metal sheets such as steel sheets, Yuen vehicles, motorcycle parts, road materials (for example, guard rails, traffic signs, etc.), tunnel materials (for example, side wall boards), ships,
  • thermosetting composition of the present invention can be used for, for example, paints, inks, paints, and molded articles.
  • the coating film performance of the coating film obtained from the coating composition comprising the thermosetting composition of the present invention was determined as follows.
  • Non-volatile content 50, dried at 0.1 mmHg for 3 hours
  • Polycarboxylic acid compound A-2 (a) solution 272.3 parts by weight
  • each monomer of the following composition After charging the catalyst solution and sodium borate, purging with nitrogen, cooling and solidifying, and degassing, the fluoromonomer was introduced into the autoclave, and the temperature was gradually raised until the autoclave internal temperature reached 60. . Thereafter, the reaction was continued for 20 hours at the same temperature, and when the internal pressure of the autoclave dropped to 1 kcm 2 or less, the reaction was stopped by cooling.
  • the obtained resin solution was poured into a large excess of heptane to precipitate the formed resin, followed by washing and drying to obtain a fluorine-containing compound. All the obtained resins were dissolved in xylene to obtain a resin solution having a nonvolatile content of 50% by weight.
  • Methyl isobutyl ketone 20.00.0 parts by weight
  • the above resin solution was placed in a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas inlet tube, and the weight of the resin solution was 200 weights! : 4.5 parts by weight of hexahydrophthalic anhydride and 44.5 parts by weight of methyl isobutyl ketone were added, and heated under nitrogen stirring to keep 120 parts.
  • Acid value over time during the reaction The weight ratio of pyridine to water is 50 times the weight of a 9: 1 mixture, and the solution heat-treated at 90 ° for 30 minutes is titrated with a standard solution of lithium hydroxide) The reaction was terminated when the acid value of the mixture became 57 or less.
  • the obtained resin solution is a polycarboxyl compound solution having a nonvolatile content of 50% by weight.
  • a mixture having the following composition was placed in a four-necked flask similar to that of IHi, and it was stirred at room temperature. After the reaction was completed when the acid value of the mixture became 1 or less, 3 parts by weight of Kiyoword 500 (manufactured by Kyowa Danigaku Kogyo Co., Ltd.) was added, and the mixture was added at room temperature.
  • a stainless steel autoclave equipped with a stirrer was charged with each monomer, catalyst solution and sodium borate having the following composition.
  • the following fluorine-containing mono! The body was introduced into the autoclave, and the temperature was gradually raised until the internal temperature of the autoclave reached 60%. Thereafter, the reaction was continued at the same temperature for 20 hours, and when the internal pressure of the autoclave dropped to 1 kg / cm 2 or less, the reaction was stopped by cooling.
  • the obtained resin solution was poured into a large excess of heptane to precipitate the formed resin, followed by washing and drying to obtain a fluorine-containing compound B-3 in a yield of 90% by weight.
  • the number average molecular weight of the obtained resin determined by gel permeation chromatography (GPC) was 6,300. All the obtained resins were dissolved in xylene to obtain a resin solution having a nonvolatile content of 50 Jt%.
  • Manganese oxide sol dispersion (average particle size: 30 nm), solid content 30% by weight, solvent: methylisobutyl ketone 1000 parts by weight and A-163 (manufactured by Nippon Unicar Co., Ltd.) , Silane coupling agent) 40 parts by weight, heated and kept at 80 ° C for 8 hours.
  • a mixture having the composition shown in Table 5 was charged into a four-necked flask equipped with a total, a reflux condenser, and a stirrer. Acid value of the mixture is 30 or less The reaction was terminated when it became, and the product was transferred to a separating funnel after allowing to cool. The obtained product is washed with 100 parts by weight of a 100 wt% aqueous sodium hydrogen carbonate solution in a separating funnel, and then deionized in 200 parts by weight until the pH of the washing solution becomes 7 or less. Washing with water was repeated. Thereafter, molecular sieve 4A1Z16 (Wako Pure Chemical Industries, Ltd.) was added to the organic layer, and the mixture was dried at room temperature for 3 days. The compound was obtained.
  • Non-volatile content 50, dried at 0.1 mmHg for 3 hours
  • Phosphorus K Painted with Kachion No. 4200 (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) on a lead-treated soft coating to a dry film thickness of 20 wm, baked at 175 for 25 minutes, and further coated with an intermediate coating.
  • Epico No. 1500 CP sealer registered trademark, manufactured by NOF CORPORATION
  • Bellcoat No. 6000 Silver Metallic Basecoat Paint (registered trademark, manufactured by NOF Corporation) by air spray.
  • the test plate was painted at intervals of 1 minute and 30 seconds in 2 stages to a dry film thickness of 15 and set at 20 ° C for 3 minutes. Furthermore, after diluting the raw paint of the above (1) with paint thinner (xylene) to the coating viscosity (25 sec. For Ford Cup No. 4, 20), apply it to the test plate prepared by the above method by air spray. Specimens were baked at 140 and 30 minutes under curing conditions. The coating film performance is shown in Table 8. In each case, a uniform and glossy coating film was obtained. Under 140 baking conditions, excellent visibility, weather resistance, outdoor contamination, and oil resistance marker-contamination , Moisture resistance, acid resistance and adhesion.
  • paint thinner xylene
  • the raw paint of (1) was diluted with a thinner (xylene) to 1 voise (measured at 20 digits using a JIS K-5400 (1990) 4.5.3 rotational viscometer method), and sealed with 40 tips. Stored. After storage in a sealed container at 40 for 30 days, the viscosity was measured again. As shown in Table 7, almost no increase in viscosity was observed, indicating excellent storage stability.
  • Raw materials having the compositions shown in Table 10 were mixed and charged in a sand mill. The mixture was dispersed until the particle size became 10 ⁇ m or less to obtain a one-pack type filler.
  • a zinc phosphate-treated molten steel plate is coated with an undercoat paint pre-color primer SP-7 (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) with a roll coater to a dry film thickness of 5 m.
  • a test plate was prepared by baking for 40 seconds at.
  • the raw paint of the above (1) was diluted with Solvesso # 150 (produced by Etsuso Co., Ltd., aromatic petroleum naphtha) to a coating viscosity (120 seconds at Ford Cup No. 4, 20).
  • the test plate prepared by the above method was coated with a roll coater, and baked at a metal temperature of 230 at baking under curing conditions for 50 seconds to prepare a test piece.
  • the performance is shown in Table 11.In each case, a uniform and glossy coating film was obtained, and excellent weather resistance, outdoor stain resistance, oil resistance marker stain resistance, moisture resistance, acid resistance, and adhesion were observed. Indicated.
  • the raw material of Birta (1) is treated with Solbesso # 150 (produced by Etsuso Co., Ltd., aromatic petroleum naphtha) by 1 void (JIS K-5400 (1990) 4.5.3 Using rotational viscometer method) Measured at 20)), then sealed and stored at 40 ⁇ . After storage in a sealed container for 30 days at 40, the viscosity was measured again. As shown in Table 10, almost no increase in viscosity was observed, indicating excellent storage stability.
  • Titanium dioxide JR-602 trade name, manufactured by Teikoku ik Co., Ltd., rutile type titanium dioxide Comparative Example 1
  • a cationic electrodeposition material Aqua No. 4200 (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) on a powdered mild steel plate to a dry film thickness of 20 / m, and baked at 175 for 25 minutes.
  • Epoxy No. 1500CP sealer (registered trademark, manufactured by NOF CORPORATION) is applied by air spray coating to a dry film thickness of 40 / m. I baked it at 140 for 30 minutes.
  • Bellcoat No. 6000 Silver Metallic Base Coat Paint (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) was applied by air spray at intervals of 1 minute and 30 seconds and a dry film thickness of 15 on two stages.
  • the raw paint of the above (1) was diluted with thinner (xylene) to a coating viscosity (25 seconds at Ford Cup No. 4, 20) as an over-clear one-coat paint, and then applied to the test plate prepared by the above method.
  • a dry paint film thickness of 10 m was applied with an air spray, and the mixture was cured at 140 for 30 minutes to produce a test piece of a composite paint film.
  • the coating film performance is shown in Table 17 and Table 18. In each case, a uniform and glossy coating film was obtained.Under 140 baking conditions, excellent glazing, weather resistance, outdoor stain resistance, and oil resistance were obtained. Marker contamination, moisture resistance, acid resistance, and adhesion.
  • Coating film performance of the composite coating film according to an alternative coating was determined as follows c P TJP 6 2 1 1 68-
  • the surface of the test piece was rubbed 100 times with a flannel impregnated with xylene, and the change in the surface state was visually observed, and the xylene rubbing resistance was evaluated according to the following 3 ⁇ 4 ⁇ .
  • the test specimen has a little change in gloss or discoloration as compared to the original test specimen.
  • the test specimen has a little change in gloss and discoloration as compared to the original test specimen.
  • the pencil hardness was determined according to JIS K-1 5400 8.4.2.
  • a reaction vessel equipped with a stirrer, a thermometer, a flow pipe and a dropping funnel was charged with 50 parts by weight of xylene and 50 parts by weight of isobutyl acetate, and heated to 110 ° C. There, 61 parts by weight of methyl methacrylate, 19 parts by weight of butyl acrylate, 19 parts by weight of mono-2-hydroxyethyl methacrylate, 1 part by weight of methacrylic acid, 2,2'-azobis (2-methylbutyronitrile ) The mixture of 2 parts by weight was heated over 2 hours while maintaining the reflux state from the 3 ⁇ 4T funnel.
  • the resin had a glass transition temperature of 50, a number average molecular weight of 4,800, a hydroxyl value of 80 mgKOH / g and an acid value of 7 mgKOHZg.
  • Resin solutions were produced in the same manner as in Production Example 1 using the types and amounts of solvents, monomers and polymerization initiators shown in Tables 19 to 22.
  • Tables 19 to 22 show the physical properties of the obtained resin.
  • FM-2 £ 100% prolatataton-modified hydroxy methacrylate (trade name, manufactured by Daicel Corporation)
  • FM-2 ⁇ -force prolacton-modified hydroxymethacrylate (trade name, manufactured by Daicel Corporation)
  • FM-2 £ 100% prolactone-modified hydroxy methacrylate (trade name, manufactured by Daicel Corporation)
  • FM—2 ⁇ -force prolacton-modified hydroxy methacrylate (trade name, manufactured by Daicel Corporation)
  • the glass transition i3 ⁇ 4 of the obtained resin was 50 ° C, the number average molecular weight was 4,000, the hydroxyl value was 100 mgKOHZg, and the acid value was 10 mg K0HZg.
  • Phosphorus-treated mild steel plate is electrodeposited with cationic electrocoating material Aqua No. 4200 (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) so as to have a dry film thickness of 20 // m, baked at 175 for 25 minutes, Epico No. 1500 CP sealer (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) was applied by air spray coating to a dry film thickness of 40 m, and baked at 140 for 30 minutes. Then, apply Bellcoat No. 6000 Silver Metallic Basecoat Paint (registered trademark, manufactured by NOF Corporation) by air spray.
  • Aqua No. 4200 registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.
  • Epico No. 1500 CP sealer registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.
  • Bellcoat No. 6000 Silver Metallic Basecoat Paint registered trademark, manufactured by NOF Corporation
  • a test plate was prepared by coating at an interval of 1 minute and 30 seconds with a dry film thickness of 15 / m in two stages and setting at 20 for 3 minutes. Further, after diluting the raw paint of the above (1) with a thinner (xylene) to a coating viscosity (25 seconds at Ford Cup No. 4, 20), spray the test paint prepared by the above method with air spray. It was baked under a curing condition of 80 minutes for 30 minutes to prepare a test piece of the composite coating film. The coating performance is shown in Table 29, and a uniform and glossy coating was obtained. Under 80 baking conditions, excellent 60 ° gloss, glazing, weather resistance, moisture resistance, and resistance to heat were obtained. It showed xylene rubbing properties, acid resistance, alkali resistance, magic stain resistance, pencil hardness, and adhesion.
  • Duranate 24 A-100 Hexamethylene diisocyanate polymer manufactured by Asahi Kabushiki FiJDl Co., Ltd.
  • Desmodur BL-3175 block-type hexamethylene diisocyanate polymer manufactured by Sumitomo Bayer Urethane Co., Ltd. Table 24
  • Example 26 27 28 29 kind Production Example If; Production Example 1 ⁇ ; Production Example 1 f Production Example 18 Resin solution
  • Na cure 4054 Phosphoric acid curing catalyst manufactured by King Industry Co., Ltd. Table 28
  • Example 42 43 44 45 46 Type Production Example 16 Production Example 17 Production Example 18 Production Example 1S Production Example 20 Resin solution
  • BYK 358 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Curing catalyst Nacure 4054 0.1 0.1 0.1 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Acryl melamine (solids weight ratio) 83/17 77/23 77/23 91/9 70/30 Sol surface shape Z Total solids (wt%) 23.5 19.1 19.1 10.4 20.1 Temperature (te) 140 130 120 140 140 Baking or forced drying
  • Tinuvin 292 manufactured by Ciba-Gaigi, hindered amine antioxidant
  • ⁇ -358 manufactured by Big Chemie, a leveling agent
  • SCAT-8 Synthesis of three shared machines
  • tin-based curing catalyst manufactured by Co., Ltd.
  • duranate THA-100 a polymer of hexamethylene diisosinate, manufactured by Asahi Kabushiki Kaisha H.
  • a paint containing an inorganic sol was prepared by mixing the parts by weight.
  • No.4200 (registered trademark, Nippon Yushi Co., Ltd.) is electrodeposited to a dry film thickness of 2 O ⁇ m, baked at 175 for 25 minutes, and further coated with an intermediate paint Epiko No. 150 CP Sealer (registered trademark) And Nippon Yushi Co., Ltd.) were applied by air spraying to a dry film thickness of 40 m, and baked at 140 ° C for 30 minutes. Then, Bellcoat No. 600 Silver Metallic Basecoat Paint (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) was sprayed with an air spray at intervals of 1 minute and 30 seconds and a dry film thickness of 15 / ⁇ m on two stages.
  • Epiko No. 150 CP Sealer registered trademark
  • Bercoat No. 600 a clear coat paint composed of acryl resin Z aminoplast resin paint No. 600 Clear Paint (registered trademark, Japan Acryl resin / Aminoplast resin weight ratio: 70/30), manufactured by Yushi Co., Ltd., is applied by air spraying to a dry film thickness of 30 / m, and cured at 140 for 30 minutes. Bake on condition.
  • the raw paint of the above (1) was prepared with its own method after the paint viscosity (Ford Cup No. 4, 25 seconds with Ford Cup No. 4, 20 seconds) with thinner (xylene).
  • the board was painted by air spray and baked under a curing condition of 80 minutes and 30 minutes to prepare a test piece of a composite coating film.
  • the coating film performance is shown in Table 34.A uniform and glossy coating film was obtained, and excellent 60 ° gloss, glazing, weather resistance, moisture resistance, and xylene rubbing were obtained under a baking condition of 80 °. Resistance, acid resistance, alkali resistance, magic stain resistance, pencil hardness, and adhesion.
  • Tables 34 to 38 show the baking conditions and coating film performance of the overclear coat.In each case, a uniform and glossy coating film was obtained, and the curing shown in Tables 23 to 28 Under the conditions, it exhibited excellent 60 ° gloss, glazing, weather resistance, moisture resistance, xylene rubbing resistance, acid resistance, alkali resistance, magic stain resistance, pencil hardness, and adhesion.
  • thermosetting composition of the present invention provides a cured product having excellent chemical performance, physical performance, stain resistance, stain removal property, weather (light) resistance, chemical resistance and moisture resistance, and excellent storage stability.
  • it is suitably used for paints, inks, agents, molded articles, and the like.
  • top-coat paint when used as a top-coat paint, it has a low emission of organic solvents and can be applied with a paint finish with excellent finish appearance.
  • clear paint or clear paint for composite coatings When the thermosetting composition or the substitute paint of the present invention is used, it has not only excellent appearance, but also excellent weather resistance, stain resistance, stain removal property, chemical resistance, and moisture resistance.
  • a composite coating film can be obtained. Therefore, it is extremely useful in the field of industrial coatings such as automotive coatings and pre-coated steel sheets.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)
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Abstract

Cette invention concerne une composition thermodurcissable contenant les éléments suivants en qualité d'ingrédients principaux: (A) un composé dont la molécule comprend au moins deux groupes carboxyle bloqués par un groupe hétérocyclique possédant un groupe éther de vinyle, un groupe thio éther de vinyle, ou une double liaison vinylique contenant un hétéroatome oxygène ou soufre; (B) un composé dont la molécule comprend au moins deux groupes fonctionnels réactifs capables de former une liaison chimique avec le groupe fonctionnel susmentionné; et (C) une dispersion d'un ou de plusieurs sols d'oxyde non organique choisis parmi des sols d'oxyde d'aluminium, d'oxyde de silicium, d'oxyde de zirconium et d'oxyde d'antimoine. Cette composition peut éventuellement contenir (D) un catalyseur acide latent sur le plan thermique et devenant actif lors du durcissement thermique. Les films de revêtement obtenus à partir de cette composition possèdent non seulement une excellente apparence, mais aussi des qualités de résistance aux intempéries, à la coloration, aux produits chimiques, à l'humidité, et aux taches.
PCT/JP1996/002971 1995-10-13 1996-10-14 Composition thermodurcissable, procede de revetement de finition et articles comportant ce revetement WO1997013809A1 (fr)

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EP96933638A EP0805186B1 (fr) 1995-10-13 1996-10-14 Composition thermodurcissable, procede de revetement de finition et articles comportant ce revetement
KR1019970702389A KR100237105B1 (ko) 1995-10-13 1996-10-14 열경화성 조성물, 도장마무리방법 및 도장물품
DE69621423T DE69621423T2 (de) 1995-10-13 1996-10-14 Hitzehärtbare zusammensetzung, verfahren zum endlackieren und beschichtete gegenstände
US08/849,545 US6103387A (en) 1995-10-13 1996-10-14 Thermosetting compositions, methods of coating and coated articles
CA002207790A CA2207790C (fr) 1995-10-13 1996-10-14 Composition thermodurcissable, procede de revetement de finition et articles comportant ce revetement
JP51013697A JP3931348B2 (ja) 1995-10-13 1996-10-14 熱硬化性組成物、塗装仕上げ方法および塗装物品
KR1019997004669A KR100237104B1 (ko) 1995-10-13 1999-05-26 도장마무리방법 및 도장물품

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JP7/291924 1995-10-13
JP7/332541 1995-11-29
JP33254195 1995-11-29
JP8/27390 1996-01-23
JP2739096 1996-01-23
JP2739196 1996-01-23
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US6242046B1 (en) * 1998-04-21 2001-06-05 Basf Nof Coatings Company, Limited Stainproof-treating agent, method for stainproof-treating and stainproof-treated article
JP3308279B2 (ja) 1998-04-21 2002-07-29 日本油脂ビーエーエスエフコーティングス株式会社 防汚処理剤、防汚処理方法及び防汚処理物品
JP2002194164A (ja) * 2000-12-27 2002-07-10 Daikin Ind Ltd 低誘電性の絶縁膜及びこれを使用した集積回路構造体
US6875513B2 (en) 2002-03-14 2005-04-05 Nissan Motor Co., Ltd. Top coat for outer panel of automotive vehicle, coating process therefor, and coat film formed thereby
JP2006243153A (ja) * 2005-03-01 2006-09-14 Nof Corp 紫外線吸収性保護膜用樹脂組成物
WO2018079775A1 (fr) * 2016-10-31 2018-05-03 旭硝子株式会社 Composition de revêtement pour élément intérieur de véhicule, élément intérieur de véhicule et procédé de fabrication d'élément intérieur de véhicule

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ES2177807T3 (es) 2002-12-16
JP3931348B2 (ja) 2007-06-13
DE69621423T2 (de) 2002-10-10
DE69621423D1 (de) 2002-07-04
KR100237105B1 (ko) 2000-01-15
EP0805186A4 (fr) 1998-12-09
EP0805186B1 (fr) 2002-05-29
TW434299B (en) 2001-05-16
US6103387A (en) 2000-08-15
EP0805186A1 (fr) 1997-11-05

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